The multiplicity of distinct grain boundary configurations in polycrystals has made it difficult to determine the relative frequency with which each configuration is adopted. As a result, the physiochemical properties of each boundary and the influence of the distribution of boundaries on macroscopic materials properties are not well understood. Using a semiautomated system, we have measured all five macroscopically observable degrees of freedom of 4.1 × 106 boundary plane segments making up 5.2 × 106μm2 of grain boundary interface area in a magnesia polycrystal. Our observations demonstrate that not all grain boundary configurations occur with the same frequency and that the relative free energies of the different interfacial configurations influence the population distribution. Furthermore, the results indicate that relative grain boundary energies can be estimated based on the free surface energies.